CN111936564B - Prepreg and method for producing same - Google Patents

Prepreg and method for producing same Download PDF

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Publication number
CN111936564B
CN111936564B CN201980022850.2A CN201980022850A CN111936564B CN 111936564 B CN111936564 B CN 111936564B CN 201980022850 A CN201980022850 A CN 201980022850A CN 111936564 B CN111936564 B CN 111936564B
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prepreg
epoxy resin
resin composition
viscosity
hours
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CN111936564A (en
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水泽知希
藤原隆行
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Toray Industries Inc
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Toray Industries Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/02—Polyglycidyl ethers of bis-phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/04—Epoxynovolacs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2463/02—Polyglycidyl ethers of bis-phenols

Abstract

The invention provides a prepreg which is excellent in handleability in a short time and at a low pressure in the attaching and laminating operations. To solve the above problem, the present invention includes the following configurations. A prepreg comprising a reinforcing fiber and an epoxy resin composition, wherein the fiber content of the prepreg is 90 mass% or less and the following conditions (a) and (b) are satisfied. (a) When the average thickness of the prepreg is D (wherein D is 3 [ mu ] m or more), the viscosity of the epoxy resin composition present in a region (I) having a depth of D/4 to 3D/4 from the surface on one side of the prepreg at 25 ℃ is 50,000Pa.s or more and 300,000Pa.s or less. (b) The viscosity of the epoxy resin composition present in at least one site (II) of the sites (II) located at a depth of 0.5 [ mu ] m from the surface of each of both surfaces of the prepreg at 25 ℃ is 10,000pas or more and 40,000pas or less.

Description

Prepreg and method for producing same
Technical Field
The present invention relates to a prepreg which is an intermediate substrate for producing a fiber-reinforced composite material suitable for sports applications, aerospace applications, general industrial applications, and the like, and which is excellent in handling properties in attachment and lamination operations, particularly high adhesion of the surface, and a method for producing the same.
Background
Fiber-reinforced composite materials composed of reinforcing fibers and a matrix resin are lightweight, have high strength and high rigidity, and are therefore widely used for sports applications and the like, aerospace applications, general industrial applications and the like. In many cases, in applications for sports, a reinforcing fiber composite material is molded into a tubular body as in a golf club, a fishing rod, a bicycle frame, or the like, and a method is widely known in which a core material such as a core rod is wound with a necessary amount of a prepreg to form a laminate, and then the prepreg is cured by heating to take out the core material to obtain a tubular body.
In such a molding method, among the handling properties of the prepreg, the adhesiveness (tack) of the prepreg is particularly important, and if the adhesiveness is insufficient, the adhesion between the core material and the prepreg or the prepreg is deteriorated, and peeling or lifting occurs in the laminate. In particular, in molding of a fishing rod, a bicycle frame, and the like, prepregs are often attached to a core material by manual operation, and there is a demand for easy attachment in a short time and at a low pressure even by manual operation from the viewpoint of operability and operation efficiency. Patent documents 1 to 3 propose methods of disposing a resin layer having a high viscosity at room temperature on the surface of a prepreg as a method of improving the adhesiveness of the prepreg.
Prior patent literature
Patent document
Patent document 1: japanese patent laid-open No. 2010-229211
Patent document 2: japanese patent laid-open publication No. 2006-264137
Patent document 3: japanese patent laid-open publication No. 2011-190430
Disclosure of Invention
Problems to be solved by the invention
The methods of patent documents 1 to 3 are suitable for performing the attaching operation by applying sufficient time and pressure, but are not suitable for attaching in a short time and at a low pressure. In general, in order to improve the adhesiveness of a prepreg under a short time and a low pressure, a method of reducing the viscosity of a resin is sometimes adopted, but when a low-viscosity resin is disposed on the surface of the prepreg, there is a problem that the surface layer resin sinks down into the interior of the prepreg more quickly, and the adhesiveness of the prepreg is greatly reduced with the passage of time.
Accordingly, an object of the present invention is to provide a prepreg which is excellent in handleability in a short time and at a low pressure in the attaching and laminating operations.
Means for solving the problems
In order to solve the above problems, the prepreg of the present invention has the following configuration.
A prepreg having a reinforcing fiber and an epoxy resin composition, wherein the fiber content of the prepreg is 90 mass% or less, and the following conditions (i) and (ii) are satisfied.
(i) The initial prepreg tack is 1.4kgf or more.
(ii) The prepreg has a tack of 0.7kgf or more after 72 hours.
Alternatively, the prepreg of the present invention has the following configuration. A prepreg having a reinforcing fiber and an epoxy resin composition, wherein the fiber content of the prepreg is 90 mass% or less and the following conditions (a) and (b) are satisfied.
(a) When the average thickness of the prepreg is D (wherein D is 3 [ mu ] m or more), the viscosity of the epoxy resin composition present in a region (I) located at a depth of D/4 to 3D/4 from the surface of the prepreg at 25 ℃ is 50,000pas or more and 300,000pas or less.
(b) The viscosity of the epoxy resin composition present in at least one of the sites (II) located at a depth of 0.5 μm from the surface of each of the two surfaces of the prepreg at 25 ℃ is 10,000pas or more and 40,000pas or less. The method for producing a prepreg of the present invention includes the following configurations.
A method for producing a prepreg, wherein an epoxy resin composition B having a viscosity at 25 ℃ of not less than 10,000Pa.s and not more than 40,000Pa.s is disposed on at least one surface of a prepreg precursor having sheet-like reinforcing fibers and an epoxy resin composition A having a viscosity at 25 ℃ of not less than 50,000Pa.s and not more than 300,000Pa.s so as to satisfy the following conditions (c), (d) and (e).
(c) The fiber content of the prepreg is 90 mass% or less.
(d) The weight per unit area of the epoxy resin composition B was 1g/m 2 As described above.
(e) The ratio of the weight per unit area of the epoxy resin composition a to the weight per unit area of the epoxy resin composition B (in the case where the epoxy resin compositions B are disposed on both sides of the prepreg precursor, the weight per unit area of the epoxy resin composition B having a large weight per unit area) is 2 or more.
Effects of the invention
According to the present invention, a prepreg having high adhesiveness which is maintained for a short time and at a low pressure for a long time can be obtained.
Detailed Description
The reinforcing fiber in the present invention is usually used as a reinforcing fiber, and can be appropriately selected depending on the required strength, and for example, carbon fiber, glass fiber, "Kevlar (registered trademark)", boron fiber, chemical fiber such as silicon carbide fiber or nylon, natural fiber, metal fiber such as alumina fiber, or the like can be used, and further, they can be combined with each other, or can be combined with other organic fiber.
Among these, carbon fibers are particularly preferably used because they have a high tensile modulus. The carbon fiber is not particularly limited, and carbon fibers such as pitch-based carbon fibers and polyacrylonitrile-based carbon fibers can be used, and these fibers may be used by mixing 2 or more kinds. Among these, polyacrylonitrile-based carbon fibers, from which prepregs having high tensile strength are easily obtained, are preferably used.
As the matrix resin used in the prepreg of the present invention, an epoxy resin composition containing an epoxy resin as a main component can be used in view of excellent balance among heat resistance, mechanical properties, and adhesion to carbon fibers.
The epoxy resin is not particularly limited, and 1 or more kinds of epoxy resins may be selected from bisphenol type epoxy resins, amine type epoxy resins, phenol Novolac type epoxy resins, cresol Novolac type epoxy resins, resorcinol type epoxy resins, phenol aralkyl type epoxy resins, naphthol aralkyl type epoxy resins, dicyclopentadiene type epoxy resins, epoxy resins having a biphenyl skeleton, isocyanate-modified epoxy resins, tetraphenylethane type epoxy resins, triphenylmethane type epoxy resins, diglycidyl aniline derivatives, and the like.
The bisphenol epoxy resin is a substance in which 2 phenolic hydroxyl groups of a bisphenol compound are glycidylated, and examples thereof include bisphenol a, bisphenol F, bisphenol AD, and bisphenol S, and halogen, alkyl-substituted products, and hydride compounds of these bisphenols. In addition, a high molecular weight material having a plurality of repeating units may be used without being limited to a monomer. Among them, bisphenol a type epoxy resins, bisphenol F type epoxy resins, and bisphenol S type epoxy resins are preferably used in view of a good balance among elastic modulus, toughness, and heat resistance.
Examples of commercially available products of the bisphenol a-type epoxy resin include "jER (registered trademark)" 825, 828, 834, 1001, 1002, 1003F, 1004AF, 1005F, 1006FS, 1007, 1009, and 1010 (manufactured by mitsubishi chemical corporation). Examples of the brominated bisphenol a-type epoxy resin include "jER (registered trademark)" 505, 5050, 5051, 5054, and 5057 (manufactured by mitsubishi chemical corporation). Examples of commercially available hydrogenated bisphenol a epoxy resins include ST5080, ST4000D, ST4100D, and ST5100 (NIPPON STEEL Chemical & Material Co., ltd., supra).
Examples of commercially available bisphenol F-type epoxy resins include "jER (registered trademark)" 806, 807, 4002P, 4004P, 4007P, 4009P, 4010P (manufactured by mitsubishi Chemical corporation, supra), "Epotote (registered trademark)" YDF2001, YDF2004 (manufactured by NIPPON STEEL Chemical & Material co., ltd., supra), and the like. Examples of the tetramethylbisphenol F-type epoxy resin include YSLV-80XY (NIPPON STEEL Chemical & Material Co., ltd.).
Examples of commercially available products of the bisphenol S type epoxy resin include "Epiclon (registered trademark)" EXA-154 (available from DIC).
Examples of the amine-type epoxy resin include tetraglycidyldiaminodiphenylmethane, triglycidylaminophenol, triglycidylaminomethanol, tetraglycidylbenzenediamine, halogen, alkynol-substituted products thereof, and hydrogenated products thereof.
Examples of the tetraglycidyl diaminodiphenylmethane include "SUMI-EPOXY (registered trademark)" ELM434 (manufactured by Sumitomo Chemical Co., ltd.), YH434L (NIPPON STEEL Chemical & Material Co., manufactured by Ltd.), "jER (registered trademark)" 604 (manufactured by Mitsubishi Chemical Co., ltd.), "Araldite" MY720, MY721 (the above named Huntsman Advanced Materials Co., manufactured by Ltd.), and the like. Examples of triglycidyl aminophenol or triglycidyl aminocresol include "SUMI-EPOXY (registered trademark)" ELM100, ELM120 (manufactured by Sumitomo chemical Co., ltd., "Araldite" MY0500, MY0510, MY0600 (manufactured by Huntsman Advanced Materials Co., ltd., "Jer" 630 (manufactured by Mitsubishi chemical Co., ltd.), and the like. Examples of tetraglycidyl xylylenediamine and hydrogenated compounds thereof include TETRAD-X and TETRAD-C (manufactured by MITSUBISHI GAS CHEMICAL COMPANY).
Examples of commercially available products of the phenol Novolac type epoxy resin include "jER (registered trademark)" 152 and 154 (manufactured by Mitsubishi chemical corporation, supra), "Epiclon (registered trademark)" N-740, N-770, and N-775 (manufactured by DIC corporation, supra).
Examples of commercially available cresol Novolac type epoxy resins include "Epiclon (registered trademark)" N-660, N-665, N-670, N-673, N-695 (available from DIC corporation), EOCN-1020, EOCN-102S, and EOCN-104S (available from Nippon chemical Co., ltd.).
As the commercial products of the above-mentioned resorcinol type epoxy resins, there can be mentioned "Denacol (registered trademark)" EX-201 (manufactured by Nagase ChemteX Corporation) and the like.
Examples of commercially available products of the above-mentioned phenol aralkyl type epoxy resin include NC-2000 (manufactured by Nippon Kagaku Co., ltd.).
Examples of commercially available products of the naphthol aralkyl type epoxy resin include "Epotote (registered trademark)" ESN-155, "Epotote (registered trademark)" ESN-355, "Epotote (registered trademark)" ESN-375, "Epotote (registered trademark)" ESN-475V, "Epotote (registered trademark)" ESN-485, "Epotote (registered trademark)" ESN-175 (NIPPON STEEL Chemical & Material Co., ltd., supra).
Commercially available products of the dicyclopentadiene type epoxy resin include "Epiclon (registered trademark)" HP-7200, HP-7200L, HP-7200H, HP-7200HH, HP-7200HHH (see DIC Co., ltd., "Tactix (registered trademark)" 558 (Huntsman Advanced Materials Co., ltd., ltd.), XD-1000-1L, XD-1000-2L (see Japan chemical Co., ltd.), and the like.
Examples of commercially available products of the epoxy resin having a biphenyl skeleton include "jER (registered trademark)" YX4000H, YX4000, YL6616 (manufactured by mitsubishi chemical corporation, mentioned above), and NC-3000 (manufactured by japan chemical corporation).
Examples of commercially available products of the isocyanate-modified Epoxy resin include XAC4151 having an oxazolidone ring, AER4152 (Asahi Kasei Epoxy co., ltd.), and ACR1348 (manufactured by ADEKA corporation).
Examples of commercially available products of the tetraphenylethane-type epoxy resin include "jER (registered trademark)" 1031 (manufactured by mitsubishi chemical corporation) as a tetrakis (glycidyloxyphenyl) ethane-type epoxy resin.
Examples of commercially available products of the triphenylmethane type epoxy resin include "Tactics (registered trademark)" 742 (Huntsman Advanced Materials co., ltd.).
Examples of commercially available products of the diglycidyl aniline derivative include GAN (diglycidyl aniline), GOT (diglycidyl toluidine, both manufactured by japan chemicals corporation), and the like.
In the epoxy resin composition of the present invention, a curing agent is preferably used in order to improve the curability of the prepreg.
The curing agent is not particularly limited, and an amine such as an aromatic amine or an alicyclic amine, a phenol resin, dicyandiamide or a derivative thereof, an acid anhydride, a polyaminoamide, an organic acid hydrazide, or an isocyanate can be used.
Examples of the aromatic amine include xylylenediamine, diaminodiphenylmethane, phenylenediamine, and diaminodiphenylsulfone.
Examples of the alicyclic amine include isophoronediamine and diphenylmethanediamine (Mensenendiamine).
Examples of the phenol resin include resins obtained by condensation of phenols such as phenol, cresol, xylenol, tert-butylphenol, nonylphenol, cashew nut oil, lignin, resorcinol, and catechol with aldehydes such as formaldehyde, acetaldehyde, and furfural, and examples of the phenol resin include Novolac resin and Resol resin (Resol resin). The Novolac resin is obtained by reacting phenol with formaldehyde in the presence of an acid catalyst such as oxalic acid under conditions of equivalent amount or excess amount of phenol. The resol resin is obtained by reacting phenol with formaldehyde in the presence of a basic catalyst such as sodium hydroxide, ammonia, or an organic amine under conditions of an equivalent amount or an excess amount of formaldehyde. Examples of commercially available phenol resins include "sumite resin (registered trademark)" (manufactured by Sumitomo Bakelite co., ltd.), \ 12424124881248303 (manufactured by yoro chemical industries, ltd.), "AV LIGHT (registered trademark)" (manufactured by asahi organic materials industries, ltd.).
Examples of commercially available products of the dicyanodiamide include DICY7 and DICY15 (manufactured by mitsubishi chemical corporation).
In addition, in sports applications such as golf clubs, fishing rods, bicycles, and the like, curing at a low temperature in a short time is desired, and therefore, it is preferable that the degree of curing of the prepreg at 130 ℃ for 2 hours is 95% or more. The degree of cure C [% ] of the prepreg as referred to herein is calculated by the following formula, using a differential scanning calorimeter (for example, DSC 8500, perkinelmer) in which Δ H represents the heat generation by curing when the uncured prepreg is simply heated from 50 ℃ at a heating rate of 40 ℃/min, and Δ H represents the heat generation by curing when the prepreg heated at 130 ℃ for 2 hours is simply heated from 50 ℃ at a heating rate of 40 ℃/min.
C＝(ΔH-ΔH’)/ΔH×100 [％]。
In order to achieve a degree of curing of 95% or more when the prepreg is cured at 130 ℃ for 2 hours, a curing accelerator is preferably used in the epoxy resin composition.
Examples of the curing accelerator include urea compounds, tertiary amines and salts thereof, imidazoles and salts thereof, triphenylphosphine or derivatives thereof, metal carboxylates, lewis acids, bronsted acids and salts thereof, and the like. Among them, a urea compound is preferably used in view of the balance between storage stability and catalyst ability.
Examples of the urea compound include N, N-dimethyl-N '- (3, 4-dichlorophenyl) urea, tolylbis (dimethylurea), 4' -methylenebis (phenyldimethylurea), and 3-phenyl-1, 1-dimethylurea. Commercially available products of urea compounds include DCMU99 (manufactured by Hodogaya Chemical co. Ltd.), "Omicure (registered trademark)" 24, 52, and 94 (manufactured by Emerald Performance Materials, LLC).
The epoxy resin composition of the present invention may contain a thermoplastic resin, inorganic particles, an inorganic filler, and the like.
The thermoplastic resin may be blended with a thermoplastic resin soluble in an epoxy resin, rubber particles, organic particles such as thermoplastic resin particles, or the like. As the thermoplastic resin soluble in the epoxy resin, a thermoplastic resin having a hydrogen bonding functional group which can be expected to improve the adhesion between the resin and the reinforcing fiber is preferably used. Examples of the thermoplastic resin soluble in the epoxy resin and having a hydrogen-bonding functional group include a thermoplastic resin having an alcoholic hydroxyl group, a thermoplastic resin having an amide bond, a thermoplastic resin having a sulfonyl group, and the like.
Examples of the thermoplastic resin having an alcoholic hydroxyl group include polyvinyl acetal resins such as polyvinyl formal and polyvinyl butyral, polyvinyl alcohol, and phenoxy resins. Examples of the thermoplastic resin having an amide bond include polyamide, polyimide, and polyvinylpyrrolidone. The thermoplastic resin having a sulfonyl group may be polysulfone. The polyamide, polyimide, and polysulfone may have a functional group such as an ether bond or a carbonyl group in the main chain. The polyamide may have a substituent on the nitrogen atom of the amide group.
Examples of commercially available thermoplastic resins that are soluble in epoxy resins and have a hydrogen-bonding functional group include Denka butyl resin, "Denka formal (registered trademark)" (manufactured by electrochemical INDUSTRIES, ltd.), "Vinylec (registered trademark)" (manufactured by "CHISSO CORPORATION)", phenoxy resin, "UCAR (registered trademark)" PKHP (manufactured by Union Carbide CORPORATION), "MACROMELT (registered trademark)" (manufactured by "Henkel hakui Corp)", polyamide resin, "Amilan (registered trademark)" CM4000 (TORAY INDUSTRIES), inc., product), examples of the polyimide include "ULTEM (registered trademark)" (manufactured by General Electric co., ltd.), "matrix (registered trademark)" 5218 (Ciba co., ltd.), "sumika excel (registered trademark)" (manufactured by sumitomo chemical co., ltd.), "UDEL (registered trademark)" (Solvay Advanced Polymers co., ltd.), and "luviol sk (registered trademark)" (BSF Japan co., ltd.), examples of the polysulfone include "luviel (registered trademark)".
Further, acrylic resins have high compatibility with epoxy resins, and are preferably used for controlling viscoelasticity. Examples of commercially available acrylic resins include "Dianal (registered trademark)" BR series (manufactured by mitsubishi chemical corporation), "Matsumoto Microsphere (registered trademark)" M, M100, M500 (manufactured by songbu oil & fat pharmaceuticals), and "Nanostrength (registered trademark)" E40F, M22N, and M52N (manufactured by ARKEMA).
As a first aspect of the prepreg of the present invention, there is provided a prepreg comprising a reinforcing fiber and an epoxy resin composition, wherein the prepreg has a fiber content of 90 mass% or less and satisfies the following conditions (i) and (ii).
(i) The initial prepreg tack is 1.4kgf or more.
(ii) The prepreg has a tack of 0.7kgf or more after 72 hours.
Here, the initial prepreg tack is the prepreg tack immediately after the prepreg is manufactured, or the prepreg tack immediately after the cover film is peeled when the surface of the prepreg is covered with a film-like substance for blocking the air at the time of manufacturing the prepreg; the prepreg tack value after 72 hours is the prepreg tack after leaving the surface of the prepreg from which the cover film was peeled for 72 hours in an environment of temperature 24. + -. 2 ℃ and humidity 50. + -.5 RH%. Note that, here, the so-called prepreg adhesion, 18 × 18mm can be measured by using an adhesion tester (for example, EMX-1000n imada Co., ltd., manufactured by ltd.) as follows 2 The prepreg (2) was pressed against the prepreg under a load of 0.5kgf (5N) for 0.1 second, and the resultant was stretched at a rate of 500 mm/min, and the resistance at peeling was measured. The initial prepreg adhesiveness is 1.4kgf or more and the prepreg adhesiveness after 72 hours is 0.7kgf or more, thereby maintaining the prepreg at a low pressure and short contact time for a long period of timeThe prepreg has high adhesiveness, and is excellent in adhesion when a large amount of hand operation is performed in sports applications such as golf clubs, fishing rods, and bicycles. In the present invention, good adhesion means that the initial prepreg tack (also referred to as initial tack) and the prepreg tack after 72 hours (also referred to as post-72 hour tack) are excellent.
Further, in the first embodiment of the prepreg of the present invention, the following condition (iii) is preferably satisfied.
(iii) The epoxy resin composition has an average viscosity of 45,000pas or more at 25 ℃.
Further, in the first aspect of the prepreg according to the present invention, it is preferable that the prepreg has reinforcing fibers and an epoxy resin composition, and the fiber content of the prepreg is 90% by mass or less and satisfies the following conditions (a) and (b).
(a) When the average thickness of the prepreg is D (wherein D is 3 [ mu ] m or more), the viscosity of the epoxy resin composition present in a region (I) located at a depth of D/4 to 3D/4 from the surface of the prepreg at 25 ℃ is 50,000Pa & s or more and 300,000Pa & s or less.
(b) The viscosity of the epoxy resin composition present in at least one of the sites (II) located at a depth of 0.5 μm from the surface of each of the two surfaces of the prepreg at 25 ℃ is 10,000pas or more and 40,000pas or less.
Here, the average thickness D of the prepreg can be obtained by taking an image of a cross section of the prepreg magnified by 200 times or more using a epi-illumination type optical microscope and calculating an average value of distances between surfaces at 5 positions in the lateral direction. The viscosity and storage modulus of the epoxy resin composition mean a complex viscosity η and storage modulus G' obtained by using a dynamic viscoelasticity measuring apparatus (for example, ARES G2: TA Instrument) and measuring at a frequency of 1.00Hz and a plate interval of 1mm while maintaining a measuring temperature using a parallel plate having a diameter of 8mm in upper and lower measuring jigs. The surface layer of the prepreg is partially peeled off using a tape or the like, a portion (I) having a depth of D/4 to 3D/4 from the surface is exposed while the thickness is confirmed by an epi-illumination type optical microscope, and 50mg of the resin composition is collected using a spatula or the like, whereby the viscosity and storage modulus of the epoxy resin composition existing in the portion (I) can be measured. Further, while the thickness was confirmed by an epi-illumination type optical microscope, 50mg of the resin composition was collected from the part (II) of the prepreg from the surface to the depth of 0.5 μm by using a spatula or the like, and the viscosity of the epoxy resin composition existing in the part (II) could be measured. Further, the average viscosity of the epoxy resin composition contained in the prepreg can be measured by collecting the resin composition by extracting the epoxy resin composition contained in the prepreg with a solvent such as methyl ethyl ketone and then evaporating the solvent.
In order to locally present the epoxy resin composition having a viscosity of 50,000pa · s or more and 300,000pa · s or less at 25 ℃ in the region (I) and locally present the epoxy resin composition having a viscosity of 10,000pa · s or more and 40,000pa · s or less at 25 ℃ in at least one region (II), the average thickness D of the prepreg is preferably 3 μm or more.
By setting the viscosity of the epoxy resin composition present on at least one side of the site (II) to 10,000pas or more at 25 ℃, excessive stickiness at the time of prepreg treatment can be suppressed. Further, by setting the viscosity of the epoxy resin composition existing on at least one side of the site (II) at 25 ℃ to 40,000pa · s or less, more preferably 38,000pa · s or less, and further preferably 31,000pa · s or less, the surface resins of the prepregs are easily compatible when they are bonded to each other, and high adhesiveness can be achieved in a short time and under low pressure.
By setting the viscosity of the epoxy resin composition present in the part (I) at 25 ℃ to 50,000pa · s or more, more preferably 100,000pa · s or more, and still more preferably 140,000pa · s or more, it is possible to suppress the sinking of the resin present in the part (II) into the fiber layer inside the prepreg, and to maintain high adhesiveness for a long time. Further, by setting the viscosity of the epoxy resin composition present in the region (I) at 25 ℃ to 300,000pa · s or less, the drapability of the prepreg is improved and the adhesiveness is improved.
Further, in the first aspect of the prepreg of the present invention, it is preferable that the epoxy resin composition present in at least one site (II) of the sites (II) of the prepreg has a viscosity of 10,000pa · s or more and 40,000pa · s or less at 25 ℃ and a storage modulus of 30,000pa or more and 80,000pa or less at 25 ℃. When the storage modulus at 25 ℃ is in this range, the retention of the surface resin is improved, and the prepreg once bonded is less likely to peel.
Further, in the first embodiment of the prepreg of the present invention, the degree of curing at 130 ℃ for 2 hours is preferably 95% or more. When the curing degree at 130 ℃ for 2 hours is in this range, molding at a low temperature in a short time becomes possible, and productivity is improved.
Further, in the first aspect of the prepreg of the present invention, the fiber content is preferably 60 mass% or more and 90 mass% or less. By setting the fiber content to 90 mass% or less, a prepreg having a stable shape can be obtained. Further, by setting the fiber content to 60 mass% or more, a reinforced fiber composite material that is lightweight and has excellent mechanical and physical properties such as strength and rigidity can be obtained.
Further, in the first embodiment of the prepreg of the present invention, it is preferable that the viscosity of the epoxy resin composition present in the site (I) at 80 ℃ is 1Pa · s or more and 80Pa · s or less. When the viscosity at 80 ℃ is less than 1 pas, the resin may flow toward both ends during impregnation into the reinforcing fibers, and the resin may protrude outward from the base material, thereby reducing the weight per unit area or the operation efficiency. When the viscosity at 80 ℃ exceeds 80Pa · s, impregnation into the reinforcing fibers is deteriorated, and therefore voids are often generated during molding, and the physical properties of the molded article are lowered.
In the first aspect of the prepreg according to the present invention, the reinforcing fibers are preferably carbon fibers. Among the reinforcing fibers, the carbon fibers also have a higher tensile elastic modulus, and a reinforced fiber composite material having excellent mechanical and physical properties can be obtained.
In the second aspect of the prepreg of the present invention, the fiber content of the prepreg is 90% by mass or less, and the following conditions (a) and (b) need to be satisfied.
(a) When the average thickness of the prepreg is D (wherein D is 3 [ mu ] m or more), the viscosity of the epoxy resin composition present in a region (I) located at a depth of D/4 to 3D/4 from the surface of the prepreg at 25 ℃ is 50,000pas or more and 300,000pas or less.
(b) The viscosity of the epoxy resin composition present in at least one site (II) of the sites (II) located at a depth of 0.5 [ mu ] m from the surface of each of both surfaces of the prepreg at 25 ℃ is 10,000pas or more and 40,000pas or less.
In the second embodiment of the prepreg of the present invention, the same contents as described in the first embodiment of the prepreg of the present invention can be preferably applied.
For the method of manufacturing the prepreg of the present invention, it is necessary that: a method for preparing an epoxy resin composition B having a viscosity of 10,000Pa.s or more and 40,000Pa.s or less at 25 ℃ on at least one surface of a prepreg precursor having sheet-like reinforcing fibers and an epoxy resin composition A having a viscosity of 50,000Pa.s or more and 300,000Pa.s or less at 25 ℃, so as to satisfy the following conditions (c), (d) and (e).
(c) The fiber content of the prepreg is 90 mass% or less.
(d) The weight per unit area of the epoxy resin composition B was 1g/m 2 As described above.
(e) The ratio of the weight per unit area of the epoxy resin composition a to the weight per unit area of the epoxy resin composition B (wherein the weight per unit area of the epoxy resin composition B having a larger weight per unit area is greater when the epoxy resin composition B is disposed on both sides of the prepreg precursor) is 2 or more.
The method for producing the prepreg precursor having the sheet-like reinforcing fibers and the epoxy resin composition a is not particularly limited, and a known production method can be used. Examples of the method include a wet method of dissolving an epoxy resin composition in a solvent such as methyl ethyl ketone or methanol to reduce its viscosity and impregnation, and a hot-melt method (dry method) of reducing its viscosity and impregnation by heating. The wet method is a method in which the reinforcing fiber is immersed in a solution of the epoxy resin composition and then pulled up, and the solvent is evaporated using an oven or the like. The hot-melt method is a method of impregnating a fiber base material made of reinforcing fibers with an epoxy resin composition having a low viscosity by heating as it is, or a method of preparing a film by temporarily applying an epoxy resin composition onto release paper or the like, and then laminating the film on both sides or one side of the fiber base material made of reinforcing fibers, and heating and pressing the film to impregnate the fiber base material made of reinforcing fibers with a resin. According to the hot melt method, the solvent remaining in the prepreg is substantially completely absent, and therefore, it is preferable.
The method of disposing the epoxy resin composition B on at least one surface of the prepreg precursor may be a method of directly applying the resin B to the surface of the prepreg precursor, or a method of transferring and applying a film obtained by previously applying the resin B to a release sheet or the like to the surface of the prepreg precursor. Examples of the method of applying the resin B to the prepreg precursor include a method of spraying a predetermined amount of resin while controlling the coating weight per unit area, such as blade coating, die coating, lip coating, and gravure coating. As a method for manufacturing a resin film in advance, the following method is used: a method of coating the resin B on a release sheet by the above-mentioned blade coating, die coating, lip coating, gravure coating, or the like, or a method of controlling the weight per unit area by the roll rotation speed and the gap between rolls, such as a reverse roll coater, a top feed reverse roll coater, or the like. The method of transferring and applying the resin film prepared in advance to the prepreg precursor is not particularly limited, and examples thereof include a method of attaching the resin surface of the resin film to one surface of the prepreg, and pressing the resin film at room temperature or by heating the resin film to such an extent that the resin is not deteriorated. In this case, the conditions for transferring and applying the film of the resin B to the prepreg precursor are preferably set to a low pressure so that the resin B is locally present on the surface side of the prepreg in order to avoid mixing with the resin a as much as possible.
In the method for producing a prepreg of the present invention, the viscosity of the epoxy resin composition a at 25 ℃ is set to 50,000pa · s or more, more preferably 100,000pa · s or more, and still more preferably 140,000pa · s or more, whereby the sinking of the resin in the surface layer of the prepreg into the fiber layer can be suppressed, and high adhesion can be maintained for a long period of time. Further, by setting the viscosity at 25 ℃ of the epoxy resin composition a to 300,000pa · s or less, the drape property of the obtained prepreg is improved and the adhesiveness is good.
In the method for producing a prepreg of the present invention, the viscosity of the epoxy resin composition B at 25 ℃ is set to 10,000pa · s or more, whereby excessive tackiness during prepreg treatment can be suppressed. Further, by setting the viscosity of the epoxy resin composition B at 25 ℃ to 40,000pa · s or less, more preferably to 38,000pa · s or less, and still more preferably to 31,000pa · s or less, when the obtained prepregs are bonded to each other, the surface resins of each other are easily compatible, and high adhesiveness can be achieved in a short time and at a low pressure.
In addition, in the method for producing a prepreg of the present invention, it is necessary that the weight per unit area of the epoxy resin composition B is 1g/m 2 As described above, the ratio of the weight per unit area of the epoxy resin composition a to the weight per unit area of the epoxy resin composition B (in the case where the epoxy resin compositions B are disposed on both sides of the prepreg precursor, the weight per unit area of the epoxy resin composition B having a large weight per unit area) is 2 or more. When the weight per unit area of the epoxy resin compositions a and B is in this range, the adhesion of the prepreg can be effectively improved, and the mechanical physical properties of the reinforced fiber composite material can be stably expressed. For the same reason, the epoxy resin composition B may be disposed only on the surface on which the adhesion is desired to be improved, and is preferably disposed on one surface as compared with both surfaces of the prepreg precursor.
The epoxy resin composition present in the part (I) and the part (III) other than the part (II) in the prepreg of the present invention is not particularly limited, but when the prepreg is obtained by the above-mentioned production method, the viscosity of the epoxy resin composition present in the part (III) at 25 ℃ is usually 10,000pa · s or more and 300,000pa · s or less.
Further, in the method for producing a prepreg of the present invention, the storage modulus of the epoxy resin composition B at 25 ℃ is preferably 30,000pa or more and 80,000pa or less. When the storage modulus at 25 ℃ of the epoxy resin composition B is in this range, the retention of the surface layer resin is improved, and a prepreg which is not easily peeled off once bonded can be obtained.
In the method for producing a prepreg of the present invention, the fiber content is preferably 60 mass% or more and 90 mass% or less. By setting the fiber content to 90 mass% or less, a prepreg having a stable shape can be obtained. Further, by setting the fiber content to 60 mass% or more, a reinforced fiber composite material that is lightweight and has excellent mechanical and physical properties such as strength and rigidity can be obtained.
Further, in the method for producing a prepreg of the present invention, the viscosity of the epoxy resin composition a at 80 ℃ is preferably 1Pa · s or more and 80Pa · s or less. When the viscosity of the epoxy resin composition a at 80 ℃ is less than 1Pa · s, the resin may flow toward both ends during impregnation into the reinforcing fibers, and the resin may protrude outward from the base material, thereby reducing the weight per unit area and the handling efficiency. When the viscosity at 80 ℃ exceeds 80Pa · s, impregnation into the reinforcing fibers is deteriorated, and therefore voids are often generated during molding, and the physical properties of the molded article are lowered.
In the method for producing a prepreg according to the present invention, the reinforcing fibers are preferably carbon fibers. Among the reinforcing fibers, the carbon fibers have a high tensile modulus of elasticity, and a reinforced fiber composite material having excellent mechanical and physical properties can be obtained.
Examples
The present invention will be described in detail below with reference to examples. The present invention is not limited to the following examples.
The matrix resin and the carbon fiber used in the examples and comparative examples are as follows.
< epoxy resin >
Bisphenol A epoxy resin ("JeR (registered trademark)" 828, manufactured by Mitsubishi chemical corporation, epoxy equivalent: 189)
Bisphenol A epoxy resin ("JeR (registered trademark)" 1001, mitsubishi chemical corporation, epoxy equivalent: 475)
Phenol Novolac type epoxy resin ("jER (registered trademark)" 154, manufactured by Mitsubishi chemical corporation, epoxy equivalent: 178)
M-aminophenol type epoxy resin ("Araldite" registered trademark) "MY0600, huntsman Advanced Materials Co., ltd., epoxy equivalent: 116).
< curing agent >
4,4' -diaminodiphenyl sulfone ("Seika Cure (registered trademark)" S, available from Hill Seika chemical industries, ltd., active hydrogen equivalent: 62)
Dicyanodiamide (DICY 7, manufactured by Mitsubishi chemical corporation, active hydrogen equivalent: 12).
< curing Accelerator >
3- (3, 4-dichlorophenyl) -1, 1-dimethylurea (DCMU 99, manufactured by Baotou chemical Co., ltd.).
< thermoplastic resin >
Polyvinyl formal ("Vinylec (registered trademark)" K, manufactured by JNC K.K.)
S-B-M copolymer ("Nanostrength (registered trademark)" M22N, manufactured by ARKEMA, S is styrene, B is 1, 4-butadiene, and M is methyl methacrylate)
Polyether sulfone ("SumikaExcel (registered trademark)" PES 5003P, manufactured by Sumitomo chemical Co., ltd.).
< reinforcing fiber >
Carbon fibers ("Torayca (registered trademark)" T700SC-12K, TORAY INDUSTRIES, INC., tensile modulus of elasticity: 230GPa, tensile strength: 4900 MPa).
Carbon fiber ("Torayca (registered trademark)" M40JB-6K, TORAY INDUSTRIES, INC. Manufactured by tensile modulus of elasticity 377GPa and tensile strength 4400 MPa).
Carbon fibers ("Torayca (registered trademark)" T1100GC-12K, TORAY INDUSTRIES, INC. Manufactured by tensile modulus 324GPa and tensile strength 7000 MPa).
< preparation of epoxy resin composition >
Epoxy resin compositions (a) to (l) were obtained by melting and kneading an epoxy resin and a thermoplastic resin using the epoxy resin, a curing agent, a curing accelerator, and a thermoplastic resin in the respective parts by mass shown in table 1, followed by cooling and adding the curing agent and the curing accelerator.
The measurement methods of various characteristics (physical properties) in the present example and comparative example are as follows.
< method for measuring average thickness >
The cross section of the prepreg obtained was enlarged by 200 times or more with a epi-illumination type optical microscope, and photographs were taken so that the upper and lower surfaces of the prepreg were placed in the visual field. The distances between the surfaces were measured at 5 positions in the transverse direction of the sectional photograph, and the average value thereof was defined as the average prepreg thickness D.
< method for measuring viscosity and storage modulus >
The surface layer of the resulting prepreg was peeled off using an adhesive tape, and while the thickness was confirmed with an epi-illumination type optical microscope, a portion (I) having a depth of D/4 to 3D/4 from the surface was exposed, and 50mg of the resin composition was collected with a spatula. Further, 50mg of the resin composition was collected from a region (II) from the surface of the prepreg to a depth of 0.5 μm by using a spatula while confirming the thickness with an epi-illumination type optical microscope. The epoxy resin composition contained in the prepreg was extracted with methyl ethyl ketone, and then the methyl ethyl ketone was evaporated to obtain a resin composition for measuring an average viscosity.
The obtained epoxy resin composition was set using a flat plate parallel plate having a diameter of 8mm in upper and lower measuring jigs by a dynamic viscoelasticity measuring apparatus (ARES G2: TA Instrument Co., ltd.) so that the distance between the upper and lower jigs was 1mm, and then the viscosity and storage modulus were measured at a frequency of 1.00Hz while maintaining the measuring temperature. The strain was 0.1% at a measurement temperature of 25 ℃ and 100% at a measurement temperature of 80 ℃.
< method for measuring degree of curing >
When the obtained prepreg was simply heated from 50 ℃ at a heating rate of 40 ℃/min using a differential scanning calorimeter (DSC 8500, perkinelmer), the detected heat generation by curing was represented by Δ H, and after the prepreg heated at 130 ℃ for 2 hours was once cooled to 50 ℃, the heat generation by curing detected when the prepreg was simply heated from 50 ℃ at a heating rate of 40 ℃/min was represented by Δ H', the degree of curing C was calculated by the following equation.
C＝(ΔH-ΔH’)/ΔH×100 [％]。
< method for measuring adhesion of prepreg >
Using an adhesion tester (EMX-1000n, imada Co., ltd., manufactured), 18 × 18mm was placed in a vacuum chamber of a vacuum chamber (vacuum chamber) 2 The prepreg of (a) was pressed against the same prepreg prepared separately for 0.1 second under a load of 0.5kgf (5N), and the resistance to peeling was measured 5 times at a rate of 500 mm/min, and the average value thereof was taken as the prepreg adhesiveness. The initial prepreg tack refers to the tack of the prepreg immediately after the prepreg is manufactured, or the tack of the prepreg immediately after the cover film is peeled off when the surface of the prepreg is covered with a film-like material for blocking the air during the manufacturing; the prepreg adhesiveness after 72 hours is the prepreg adhesiveness after leaving the surface of the prepreg from which the cover film was peeled at 24. + -. 2 ℃ and 50. + -. 5% RH of humidity for 72 hours.
< method for carrying out winding test of prepreg >
200X 200mm on SUS cylinder with diameter of 20mm in the environment of temperature 24 + -2 deg.C and humidity 50 + -5% 2 The prepreg of (2) was wound under a load of 0.5kgf for 10 seconds so that the direction in which the reinforcing fibers were aligned was at an angle of 90 ° with respect to the cylinder length direction, and the wound state of the prepreg was observed with time. When the maximum peel height of the wound portion of the prepreg is 2mm or more, it is determined that "winding peel is present".
< example 1 >
As shown in the column of example 1 in Table 2, an epoxy resin composition (a) was applied to a release paper using a coater as a resin A to prepare a resin having a weight of 44g/m per unit area 2 The resin film of (1). 2 sheets of the resin films were stacked on both sides of Torayca (registered trademark) T700SC-12K reinforcing fibers arranged in a sheet-like manner in one direction, and the epoxy resin composition (a) was impregnated with the resin films under heat and pressure to prepare a prepreg precursor. Next, an epoxy resin composition (B) was applied as resin B to a release paper using a coater to prepare a resin having a weight per unit area of 12g/m 2 The resin film of (1). 1 sheet of the resin film was stacked on one surface of the prepreg precursor, and the stack was heated and pressed to obtain a fiber basis weight of 100g/m 2 And a prepreg having a fiber mass content of 50%. The prepreg had a weight per unit area of 200g/m 2 The prepreg had an average thickness of 151 μm. The viscosities of the prepreg portion (I) at 25 ℃ and 80 ℃ were 148,900pas and 15 pas, respectively. The viscosity and storage modulus at 25 ℃ of the portion (II) on the side where the resin B was arranged were 23,800pas and 101,500Pa, respectively. Further, the viscosity of the epoxy resin composition contained in the prepreg at 25 ℃ was 124, 600 pas. The prepreg tack of the prepreg obtained was measured, and the initial tack was 2.3kgf (23N), the tack after 72 hours was 1.6kgf (16N), and the initial and 72 hours after tack were good. The winding test of this prepreg was carried out, and as a result, winding separation did not occur even after 72 hours or more had elapsed after winding, and the winding property was good. The degree of cure at 130 ℃ for 2 hours was 70%.
< example 2 >
As shown in the column of example 2 in Table 2, the weight per unit area of the resin film of resin A was set to 13g/m 2 Otherwise, a fiber basis weight of 100g/m was prepared in the same manner as in example 1 2 And a fiber mass content of 72%. The prepreg had a weight per unit area of 138g/m 2 It is lighter than example 1. Furthermore, the prepreg had an average thickness of 96 μm. The viscosities at 25 ℃ and 80 ℃ of the prepreg part (I) were respectively148,900pas and 15 pas. The viscosity and storage modulus at 25 ℃ of the site (II) were 23,800pas and 101,500Pa, respectively. Further, the viscosity of the epoxy resin composition contained in the prepreg at 25 ℃ was 118,700pas. The prepreg tack of the prepreg obtained was measured, and as a result, the initial tack was 1.5kgf (15N), the tack after 72 hours was 0.9kgf (9N), and the initial and 72 hours after tack were good. As a result of the winding test of the prepreg, winding separation did not occur even after 72 hours or more passed after winding, and the winding property was good. The degree of cure at 130 ℃ for 2 hours was 80%, and the curability was better than that of example 1.
< example 3 >
A fiber basis weight of 100g/m was prepared in the same manner as in example 2 except that the resin was changed to the resin composition (c) as described in the column of example 3 in Table 2 2 And a fiber mass content of 72%. The prepreg had a weight per unit area of 138g/m 2 The prepreg had an average thickness of 95 μm. The viscosities at 25 ℃ and 80 ℃ of the prepreg region (I) were 61,400pas and 9 pas, respectively. The viscosity and storage modulus at 25 ℃ of the site (II) were 23,800pas and 101,500Pa, respectively. Further, the viscosity of the epoxy resin composition contained in the prepreg at 25 ℃ was 52, 100 pas. The prepreg tack of the resulting prepreg was measured, and as a result, the initial tack was 1.5kgf (15N), the tack after 72 hours was 0.8kgf (8N), and the initial and 72 hours after tack were good. The winding test of this prepreg was carried out, and as a result, no winding separation occurred even after 72 hours or more had elapsed after winding, and the winding property was good. The degree of cure at 130 ℃ for 2 hours was 100%, and the curability was better than that of example 2.
< example 4 >
A fiber basis weight of 100g/m was prepared in the same manner as in example 3 except that the resin B was changed to the resin composition (d) as described in the column of example 4 in Table 2 2 And a fiber mass content of 72%. Prepreg unitThe areal weight is 138g/m 2 The prepreg had an average thickness of 95 μm. The viscosities at 25 ℃ and 80 ℃ of the prepreg region (I) were 61,400pas and 9 pas, respectively. The viscosity and storage modulus at 25 ℃ of the site (II) were 14,700pas and 28,200Pa, respectively. Further, the viscosity of the epoxy resin composition contained in the prepreg at 25 ℃ was 50,800pas. The prepreg tack of the resulting prepreg was measured, and as a result, the initial tack was 1.4kgf (14N), the tack after 72 hours was 0.7kgf (7N), and the initial and 72 hours after tack were good. The winding test of this prepreg was carried out, and as a result, no winding separation occurred even after 72 hours or more had elapsed after winding, and the winding property was good. The degree of cure at 130 ℃ for 2 hours was 100%.
< example 5 >
A fiber basis weight of 100g/m was prepared in the same manner as in example 4 except that the resin B was changed to the resin composition (e) as described in the column of example 5 in Table 2 2 And a fiber mass content of 72%. The weight per unit area of the prepreg was 138g/m 2 The prepreg had an average thickness of 96 μm. The viscosities at 25 ℃ and 80 ℃ of the prepreg part (I) were 61,400pas and 9 pas, respectively. The viscosity and storage modulus at 25 ℃ of the site (II) were 10,300pas and 76,600Pa, respectively. Further, the viscosity of the epoxy resin composition contained in the prepreg at 25 ℃ was 45,800pas. The prepreg tack of the prepreg obtained was measured, and the initial tack was 2.3kgf (23N), the tack after 72 hours was 1.1kgf (11N), and the initial and 72 hours after tack were good. The winding test of this prepreg was carried out, and as a result, no winding separation occurred even after 72 hours or more had elapsed after winding, and the winding property was good. The degree of cure at 130 ℃ for 2 hours was 100%.
< example 6 >
A fiber basis weight of 100g/m was prepared in the same manner as in example 5 except that the resin B was changed to the resin composition (f) as described in the column of example 6 in Table 2 2 Fiber mass content72% of prepreg. The prepreg had a weight per unit area of 138g/m 2 The prepreg had an average thickness of 95 μm. The viscosities at 25 ℃ and 80 ℃ of the prepreg region (I) were 61,400pas and 9 pas, respectively. The viscosity and storage modulus at 25 ℃ of the site (II) were 37,600Pa · s and 37,400Pa, respectively. Further, the viscosity of the epoxy resin composition contained in the prepreg at 25 ℃ was 54,600pas. The prepreg tack of the resulting prepreg was measured, and as a result, the initial tack was 1.7kgf (17N), the tack after 72 hours was 0.8kgf (8N), and the initial and 72 hours after tack were good. The winding test of this prepreg was carried out, and as a result, winding separation did not occur even after 72 hours or more had elapsed after winding, and the winding property was good. The degree of cure at 130 ℃ for 2 hours was 100%.
< example 7 >
A fiber basis weight of 100g/m was prepared in the same manner as in example 6 except that the resin A was changed to the resin composition (g) as described in the column of example 7 in Table 2 2 And a fiber mass content of 72%. The prepreg had a weight per unit area of 138g/m 2 The prepreg had an average thickness of 98 μm. The viscosities at 25 ℃ and 80 ℃ of the prepreg region (I) were 255,600pas and 1 pas, respectively. The viscosity and storage modulus at 25 ℃ of the site (II) were 37,600Pa · s and 37,400Pa, respectively. Further, the viscosity of the epoxy resin composition contained in the prepreg at 25 ℃ was 192,400pas. The prepreg tack of the resulting prepreg was measured, and as a result, the initial tack was 1.8kgf (18N), the tack after 72 hours was 1.2kgf (12N), and the initial and 72 hours after tack were good. The winding test of this prepreg was carried out, and as a result, winding separation did not occur even after 72 hours or more had elapsed after winding, and the winding property was good. The degree of curing at 130 ℃ for 2 hours was 100%.
< example 8 >
As shown in the column of example 8 in Table 2, the weight per unit area of the resin film of resin A was set to 23g/m 2 Otherwise, the same method as in example 7 was usedMethod for producing a fiber having a basis weight of 100g/m 2 And a fiber mass content of 63%. The prepreg had a weight per unit area of 158g/m 2 The prepreg had an average thickness of 114 μm. The viscosities of the prepreg portion (I) at 25 ℃ and 80 ℃ were 255,600pas and 1 pas, respectively. The viscosity and storage modulus at 25 ℃ of the site (II) were 37,600Pa · s and 37,400Pa, respectively. Further, the viscosity of the epoxy resin composition contained in the prepreg at 25 ℃ was 220,000pa · s. The prepreg tack of the prepreg obtained was measured, and as a result, the initial tack was 1.9kgf (19N), the tack after 72 hours was 1.4kgf (14N), and the tack was good both initially and after 72 hours. The winding test of this prepreg was carried out, and as a result, no winding separation occurred even after 72 hours or more had elapsed after winding, and the winding property was good. The degree of curing at 130 ℃ for 2 hours was 100%.
< example 9 >
As shown in the column of example 9 in Table 3, the weight per unit area of the resin film of resin A was set to 9g/m 2 The weight per unit area of the resin film of the resin B was set to 1g/m 2 Except for this, a fiber basis weight of 100g/m was produced in the same manner as in example 7 2 And a prepreg having a fiber mass content of 84%. The weight per unit area of the prepreg was 119g/m 2 The prepreg had an average thickness of 80 μm. The viscosities at 25 ℃ and 80 ℃ of the prepreg region (I) were 255,600pas and 1 pas, respectively. The viscosity and storage modulus at 25 ℃ of the site (II) were 37,600Pa · s and 37,400Pa, respectively. Further, the viscosity of the epoxy resin composition contained in the prepreg at 25 ℃ was 246,700pas. The prepreg tack of the prepreg obtained was measured, and as a result, the initial tack was 1.6kgf (16N), the tack after 72 hours was 0.8kgf (8N), and the tack was good both initially and after 72 hours. The winding test of this prepreg was carried out, and as a result, winding separation did not occur even after 72 hours or more had elapsed after winding, and the winding property was good. The degree of cure at 130 ℃ for 2 hours was 100%.
< example 10 >
A fiber basis weight of 100g/M was produced in the same manner as in example 7, except that Torayca (registered trademark) M40JB-6K was used as the reinforcing fiber in example 10 of Table 3 2 And a fiber mass content of 72%. The prepreg had a weight per unit area of 138g/m 2 The prepreg had an average thickness of 100 μm. The viscosities at 25 ℃ and 80 ℃ of the prepreg region (I) were 255,600pas and 1 pas, respectively. The viscosity and storage modulus at 25 ℃ of the site (II) were 37,600Pa · s and 37,400Pa, respectively. Further, the viscosity of the epoxy resin composition contained in the prepreg at 25 ℃ was 193,400pas. The prepreg tack of the prepreg obtained was measured, and as a result, the initial tack was 1.8kgf (18N), the tack after 72 hours was 1.0kgf (10N), and the tack was good both initially and after 72 hours. The winding test of this prepreg was carried out, and as a result, no winding separation occurred even after 72 hours or more had elapsed after winding, and the winding property was good. The degree of cure at 130 ℃ for 2 hours was 100%.
< example 11 >
A fiber having a weight per unit area of 100g/m was produced in the same manner as in example 7, except that the reinforcing fiber was Torayca (registered trademark) "T1100GC-12K as listed in the column of example 11 in Table 3 2 And a prepreg having a fiber mass content of 72%. The weight per unit area of the prepreg was 138g/m 2 The prepreg had an average thickness of 99 μm. The viscosities of the prepreg portion (I) at 25 ℃ and 80 ℃ were 255,600pas and 1 pas, respectively. The viscosity and storage modulus at 25 ℃ of the site (II) were 37,600Pa · s and 37,400Pa, respectively. Further, the viscosity of the epoxy resin composition contained in the prepreg at 25 ℃ was 194,200pas. The prepreg tack of the resulting prepreg was measured, and as a result, the initial tack was 1.8kgf (18N), the tack after 72 hours was 1.3kgf (13N), and the initial and 72 hours after tack were good. The winding test of this prepreg was carried out, and as a result, no winding separation occurred even after 72 hours or more had elapsed after winding, and the winding property was good. In addition, cure was 2 hours at 130 deg.CThe degree of curing with time was 100%.
< example 12 >
As shown in the column of example 12 in Table 3, the basis weight of the fiber was 55g/m 2 Except for this, a prepreg having a fiber mass content of 74% was produced in the same manner as in example 9. The prepreg had a weight per unit area of 74g/m 2 The prepreg had an average thickness of 51 μm. The viscosities at 25 ℃ and 80 ℃ of the prepreg region (I) were 255,600pas and 1 pas, respectively. The viscosity and storage modulus at 25 ℃ of the site (II) were 37,600Pa · s and 37,400Pa, respectively. Further, the viscosity of the epoxy resin composition contained in the prepreg at 25 ℃ was 250,300pas. The prepreg tack of the prepreg obtained was measured, and as a result, the initial tack was 1.6kgf (16N), the tack after 72 hours was 1.1kgf (11N), and the tack was good both initially and after 72 hours. The winding test of this prepreg was carried out, and as a result, no winding separation occurred even after 72 hours or more had elapsed after winding, and the winding property was good. The degree of curing at 130 ℃ for 2 hours was 100%.
< example 13 >
As shown in the column of example 13 in Table 3, the weight per unit area of the resin film of resin A was set to 6g/m 2 Except for this, a prepreg having a fiber mass content of 81% was produced in the same manner as in example 12. The prepreg had a weight per unit area of 68g/m 2 The prepreg had an average thickness of 47 μm. The viscosities at 25 ℃ and 80 ℃ of the prepreg region (I) were 255,600pas and 1 pas, respectively. The viscosity and storage modulus at 25 ℃ of the site (II) were 37,600Pa · s and 37,400Pa, respectively. Further, the viscosity of the epoxy resin composition contained in the prepreg at 25 ℃ was 241,800pas. The prepreg tack of the resulting prepreg was measured, and as a result, the initial tack was 1.6kgf (16N), the tack after 72 hours was 0.9kgf (9N), and the initial and 72 hours after tack were good. The winding test of this prepreg was carried out, and as a result, no winding separation occurred even after 72 hours or more had elapsed after winding, and the winding property was good. In addition, curing at 130 DEG CThe degree of cure at 2 hours was 100%.
< example 14 >
As shown in the column of example 14 in Table 3, 2 sheets of resin having a weight of 12g/m per unit area were used 2 The same procedure as in example 7 was repeated except that films of the epoxy resin composition (f) were stacked on both surfaces of the prepreg precursor and heated while applying pressure, to thereby prepare a prepreg having a fiber basis weight of 100g/m 2 And a fiber mass content of 67%. The prepreg had a weight per unit area of 150g/m 2 The prepreg had an average thickness of 110 μm. The viscosities of the prepreg portion (I) at 25 ℃ and 80 ℃ were 255,600pas and 1 pas, respectively. The viscosity and storage modulus at 25 ℃ of the site (II) were 37,600Pa · s and 37,400Pa, respectively. Further, the viscosity of the epoxy resin composition contained in the prepreg at 25 ℃ was 151,500pas. The prepreg tack of the prepreg obtained was measured, and as a result, the initial tack was 1.9kgf (19N), the tack after 72 hours was 1.3kgf (13N), and the tack was good both initially and after 72 hours. The winding test of this prepreg was carried out, and as a result, no winding separation occurred even after 72 hours or more had elapsed after winding, and the winding property was good. The degree of cure at 130 ℃ for 2 hours was 100%.
< example 15 >
A fiber basis weight of 100g/m was prepared in the same manner as in example 7, except that the resin B was changed to the resin composition (j) as described in the column of example 15 in Table 3 2 And a fiber mass content of 72%. The prepreg had a weight per unit area of 138g/m 2 The prepreg had an average thickness of 98 μm. The viscosities at 25 ℃ and 80 ℃ of the prepreg region (I) were 255,600pas and 1 pas, respectively. The viscosity and storage modulus at 25 ℃ of the site (II) were 30,000pas and 67,200Pa, respectively. Further, the viscosity of the epoxy resin composition contained in the prepreg at 25 ℃ was 190,000pa · s. The prepreg tack of the prepreg thus obtained was measured, and as a result, the initial tack was 2.0kgf (20N), the tack after 72 hours was 1.2kgf (12N), and the initial and after 72 hours, the tackAll were good. The winding test of this prepreg was carried out, and as a result, no winding separation occurred even after 72 hours or more had elapsed after winding, and the winding property was good. The degree of cure at 130 ℃ for 2 hours was 100%.
< example 16 >
A fiber basis weight of 100g/m was prepared in the same manner as in example 7, except that the resin B was changed to the resin composition (k) as described in the column of example 16 in Table 3 2 And a fiber mass content of 72%. The prepreg had a weight per unit area of 138g/m 2 The prepreg had an average thickness of 97 μm. The viscosities at 25 ℃ and 80 ℃ of the prepreg region (I) were 255,600pas and 1 pas, respectively. The viscosity and storage modulus at 25 ℃ of the site (II) were 33,800pas and 33,400Pa, respectively. Further, the viscosity of the epoxy resin composition contained in the prepreg at 25 ℃ was 182,300pas. The prepreg tack of the resulting prepreg was measured, and as a result, the initial tack was 1.6kgf (16N), the tack after 72 hours was 0.8kgf (8N), and the initial and 72 hours after tack were good. The winding test of this prepreg was carried out, and as a result, winding separation did not occur even after 72 hours or more had elapsed after winding, and the winding property was good. The degree of cure at 130 ℃ for 2 hours was 100%.
< example 17 >
A fiber basis weight of 55g/m was prepared in the same manner as in example 12, except that the resin B was changed to the resin composition (l) as described in the column of example 17 in Table 4 2 And a prepreg having a fiber mass content of 74%. The prepreg had a weight per unit area of 74g/m 2 The prepreg had an average thickness of 52 μm. The viscosities of the prepreg portion (I) at 25 ℃ and 80 ℃ were 255,600pas and 1 pas, respectively. The viscosity and storage modulus at 25 ℃ of the site (II) were 37,200pas and 36,600Pa, respectively. Further, the viscosity of the epoxy resin composition contained in the prepreg was 249,600pas at 25 ℃. The prepreg adhesiveness of the obtained prepreg was measured, and as a result, the initial adhesiveness was 1.6kgf (16N), and the adhesiveness after 72 hours was 11kgf (11N), the initial adhesion and the adhesion after 72 hours were good. The winding test of this prepreg was carried out, and as a result, winding separation did not occur even after 72 hours or more had elapsed after winding, and the winding property was good. The degree of curing at 130 ℃ for 2 hours was 100%.
< comparative example 1 >
As shown in the column of comparative example 1 in Table 4, an epoxy resin composition (c) was applied to a release paper using a coater as the resin A to prepare a resin having a weight of 19g/m 2 The resin film of (1). 2 sheets of the resin film were stacked on both sides of a reinforcing fiber "Torayca (registered trademark)" T700SC-12K arranged in a sheet-like manner in one direction, and the epoxy resin composition (c) was impregnated with the resin film under heat and pressure to obtain a fiber basis weight of 100g/m 2 And a prepreg having a fiber mass content of 72%. The weight per unit area of the prepreg was 138g/m 2 The prepreg had an average thickness of 94 μm. The viscosities at 25 ℃ and 80 ℃ of the prepreg region (I) were 61,400pas and 9 pas, respectively. The viscosity and storage modulus at 25 ℃ of the site (II) were 61,400pas and 161,500Pa, respectively. Further, the viscosity of the epoxy resin composition contained in the prepreg at 25 ℃ was 61,400pas. The prepreg tack of the resulting prepreg was measured, and as a result, the initial tack was 1.1kgf (11N), and after 72 hours, the tack was 0.7kgf (7N), and the initial tack was insufficient. When the winding test of this prepreg was performed, winding separation occurred within several seconds after winding, and the winding property was poor. The degree of cure at 130 ℃ for 2 hours was 100%.
< comparative example 2 >
A fiber basis weight of 100g/m was obtained in the same manner as in comparative example 2 except that the epoxy resin (e) was used as the resin A as described in the column of comparative example 2 in Table 4 2 And a fiber mass content of 72%. The prepreg had a weight per unit area of 138g/m 2 The prepreg had an average thickness of 94 μm. The prepreg sections (I) had viscosities of 10,300pas and 48 pas at 25 ℃ and 80 ℃. In addition, the viscosity and storage modulus at 25 ℃ of the site (II)10,300pa · s and 76,600pa, respectively. Further, the viscosity of the epoxy resin composition contained in the prepreg at 25 ℃ was 10,300pas. The prepreg tack of the prepreg obtained was measured, and as a result, the initial tack was 2.1kgf (21N) and the tack after 72 hours was 0.3kgf (3N), and although the initial tack was good, the tack after 72 hours was insufficient. When the winding test of this prepreg was performed, the winding peeling occurred within 24 hours after winding, and the winding property was slightly poor. The degree of curing at 130 ℃ for 2 hours was 100%.
< comparative example 3 >
The same procedures as in example 5 were repeated except that the epoxy resin (f) was used as the resin A as described in comparative example 3 in Table 4 to obtain a fiber basis weight of 100g/m 2 And a fiber mass content of 72%. The weight per unit area of the prepreg was 138g/m 2 The prepreg had an average thickness of 96 μm. The viscosities at 25 ℃ and 80 ℃ of the prepreg region (I) were 37,600pas and 2 pas, respectively. The viscosity and storage modulus at 25 ℃ of the site (II) were 10,300pas and 76,600Pa, respectively. Further, the viscosity of the epoxy resin composition contained in the prepreg at 25 ℃ was 29,600pas. The prepreg tack of the prepreg obtained was measured, and as a result, the initial tack was 2.1kgf (21N), and the tack after 72 hours was 0.6kgf (6N), which significantly deteriorated the tack after 72 hours as compared with example 5. When the winding test of this prepreg was performed, the winding peeling occurred within 48 hours after winding, and the winding property was slightly poor. The degree of cure at 130 ℃ for 2 hours was 100%.
< comparative example 4 >
A fiber basis weight of 100g/m was obtained in the same manner as in example 7 except that the epoxy resin (c) was used as the resin B as described in comparative example 4 of Table 4 2 And a fiber mass content of 72%. The weight per unit area of the prepreg was 138g/m 2 The prepreg had an average thickness of 98 μm. The viscosities at 25 ℃ and 80 ℃ of the prepreg region (I) were 37,600pas and 2 pas, respectively. This is achieved byIn addition, the viscosity and storage modulus at 25 ℃ of the site (II) were 61,400pas and 161,500Pa, respectively. Further, the viscosity of the epoxy resin composition contained in the prepreg at 25 ℃ was 201,500pas. The prepreg tack of the obtained prepreg was measured, and as a result, the initial tack was 1.2kgf (12N), and after 72 hours, the tack was 0.7kgf (7N), and the initial tack was significantly deteriorated as compared to example 7. When the winding test of this prepreg was performed, winding separation occurred within several seconds after winding, and the winding property was poor. The degree of cure at 130 ℃ for 2 hours was 100%.
< comparative example 5 >
A fiber basis weight of 100g/m was obtained in the same manner as in comparative example 4 except that the epoxy resin (h) was used as the resin A as described in the column of comparative example 5 in Table 4 2 And a prepreg having a fiber mass content of 72%. The prepreg had a weight per unit area of 138g/m 2 The prepreg had an average thickness of 97 μm. The viscosities at 25 ℃ and 80 ℃ of the prepreg portion (I) were 7,800pas and 7 pas, respectively. The viscosity and storage modulus at 25 ℃ of the site (II) were 61,400pas and 161,500Pa, respectively. Further, the viscosity of the epoxy resin composition contained in the prepreg at 25 ℃ was 27,300pas. The prepreg tack of the prepreg obtained was measured, and as a result, the initial tack was 0.9kgf (9N), and the tack after 72 hours was 0.5kgf (5N), which further worsened the adhesiveness as compared with comparative example 4. When the winding test of this prepreg was performed, winding separation occurred within several seconds after winding, and the winding property was poor. The degree of curing at 130 ℃ for 2 hours was 100%.
< comparative example 6 >
The same procedure as in comparative example 4 was repeated except that the epoxy resin (i) was used as the resin A as described in comparative example 6 of Table 4 to obtain a fiber basis weight of 100g/m 2 And a prepreg having a fiber mass content of 72%. The prepreg had a weight per unit area of 138g/m 2 The prepreg had an average thickness of 98 μm. The prepreg has a site (I) having viscosities of 255,600pas and 1 pas at 25 ℃ and 80 ℃ respectively. The viscosity and storage modulus at 25 ℃ of the site (II) were 147,200pas and 92,500Pa, respectively. Further, the viscosity of the epoxy resin composition contained in the prepreg at 25 ℃ was 228,500pas. The prepreg tack of the prepreg obtained was measured, and as a result, the initial tack was 1.1kgf (11N), and the tack after 72 hours was 0.7kgf (7N), and the initial tack was inferior to that of comparative example 4. When the winding test of this prepreg was performed, winding separation occurred within several seconds after winding, and the winding property was poor. The degree of cure at 130 ℃ for 2 hours was 100%.
< comparative example 7 >
As shown in the column of comparative example 7 in Table 4, the basis weight of the resin film of resin A was set to 4g/m 2 Otherwise, the same procedure as in example 10 was repeated to attempt to obtain a fiber basis weight of 100g/m 2 And a prepreg having a fiber mass content of 92%, but the prepreg could not be formed into a shape as a prepreg and could not be produced.
[ Table 1]
Figure BDA0002704534760000301
[ Table 2]
Figure BDA0002704534760000311
[ Table 3]
Figure BDA0002704534760000321
[ Table 4]
Figure BDA0002704534760000331
Industrial applicability
The prepreg of the present invention can maintain high adhesiveness for a long time under a short time and a low pressure, and therefore, is excellent in handling property and is preferably used particularly for sports and leisure uses such as fishing rods and bicycle frames to which many attachments are manually applied during molding.

Claims (12)

1. A prepreg having reinforcing fibers and an epoxy resin composition, wherein the fiber content of the prepreg is 90 mass% or less and the following conditions (a) and (b) are satisfied,
(a) The viscosity of an epoxy resin composition present in a region (I) located at a depth of D/4 to 3D/4 from the surface of a prepreg is 50,000Pa.s or more and 300,000Pa.s or less at 25 ℃, where D is 3 [ mu ] m or more, where D is defined as D,
(b) The viscosity of the epoxy resin composition present in at least one of the sites (II) located at a depth of 0.5 μm from the surface of each of the two surfaces of the prepreg at 25 ℃ is 10,000pas or more and 40,000pas or less.
2. The prepreg according to claim 1, which satisfies the following conditions (i) and (ii),
(i) The initial prepreg adhesiveness is 1.4kgf or more,
(ii) The prepreg adhesiveness after 72 hours was 0.7kgf or more.
3. The prepreg according to claim 1 or 2, wherein the epoxy resin composition of the site (II) having a viscosity of 10,000pa · s or more and 40,000pa · s or less at 25 ℃ has a storage modulus of 30,000pa or more and 80,000pa or less at 25 ℃.
4. The prepreg according to claim 1 or 2, wherein a curing degree when cured at 130 ℃ for 2 hours is 95% or more.
5. The prepreg according to claim 1 or 2, wherein the fiber content is 60% by mass or more and 90% by mass or less.
6. The prepreg according to claim 1 or 2, wherein the viscosity of the epoxy resin composition present in the part (I) of the prepreg at 80 ℃ is 1Pa s or more and 80Pa s or less.
7. The prepreg according to claim 1 or 2, wherein the reinforcing fibers are carbon fibers.
8. A method for producing a prepreg, wherein an epoxy resin composition B having a viscosity of 10,000Pa s or more and 40,000Pa s or less at 25 ℃ is disposed on at least one surface of a prepreg precursor having sheet-like reinforcing fibers and an epoxy resin composition A having a viscosity of 50,000Pa s or more and 300,000Pa s or less at 25 ℃ so as to satisfy the following conditions (c), (d) and (e),
(c) The fiber content of the prepreg is 90 mass% or less,
(d) The weight per unit area of the epoxy resin composition B was 1g/m 2 In the above-mentioned manner,
(e) The ratio of the weight per unit area of the epoxy resin composition A to the weight per unit area of the epoxy resin composition B is 2 or more,
when the epoxy resin composition B is disposed on both surfaces of the prepreg precursor, the weight per unit area is the weight per unit area of the epoxy resin composition B having a large weight per unit area.
9. The method for producing a prepreg according to claim 8, wherein the epoxy resin composition B has a storage modulus at 25 ℃ of 30,000Pa or more and 80,000Pa or less.
10. The method of producing a prepreg according to claim 8 or 9, wherein the fiber content is 60 mass% or more and 90 mass% or less.
11. The method for producing a prepreg according to claim 8 or 9, wherein the viscosity of the epoxy resin composition a at 80 ℃ is 1Pa · s or more and 80Pa · s or less.
12. The method of manufacturing a prepreg according to claim 8 or 9, wherein the reinforcing fiber is a carbon fiber.
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